Abstract
Alkylation of benzene with carbon dioxide and hydrogen to produce toluene and xylene could increase the added-value of surplus benzene as well as relieve environmental problems like green-house effect. In this work, the alkylation benzene with carbon dioxide and hydrogen reaction was proceeded by using the mixture of zinc-zirconium oxide and HZSM-5 as bifunctional catalyst. The equivalent of Zn/Zr = 1 displays the best catalytic performance at 425 °C and 3.0 MPa, and benzene conversion reaches 42.9% with a selectivity of 90% towards toluene and xylene. Moreover, the carbon dioxide conversion achieves 23.3% and the carbon monoxide selectivity is lower than 35%, indicating that more than 50% carbon dioxide has been effectively incorporated into the target product, which is the best result as far as we know. Combined with characterizations, it indicated that the Zn and Zr formed a solid solution under specific conditions (Zn/Zr = 1). The as-formed solid solution not only possesses a high surface area but also provides a large amount of oxygen vacancies. Additionally, the bifunctional catalyst has excellent stabilities that could keep operating without deactivation for at least 80 h. This work provides promising industrial applications for the upgrading of aromatics.
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References
Zhong J, Yang X, Wu Z, Liang B, Huang Y, Zhang T. State of the art and perspectives in heterogeneous catalysis of CO2 hydrogenation to methanol. Chemical Society Reviews, 2020, 49(5): 1385–1413
Bushuyev O S, De Luna P, Dinh C T, Tao L, Saur G, Van De Lagemaat J, Kelley S O, Sargent E H. What should we make with CO2 and how can we make it? Joule, 2018, 2(5): 825–832
Bonura G, Cordaro M, Cannilla C, Mezzapica A, Spadaro L, Arena F, Frusteri F. Catalytic behaviour of a bifunctional system for the one step synthesis of DME by CO2 hydrogenation. Catalysis Today, 2014, 228: 51–57
Kattel S, Liu P, Chen J G. Tuning selectivity of CO2 hydrogenation reactions at the metal/oxide interface. Journal of the American Chemical Society, 2017, 139(29): 9739–9754
Liu J, Zhang A, Jiang X, Liu M, Sun Y, Song C, Guo X. Selective CO2 hydrogenation to hydrocarbons on Cu-promoted Fe-based catalysts: dependence on Cu-Fe interaction. ACS Sustainable Chemistry & Engineering, 2018, 6(8): 10182–10190
Wang J, You Z, Zhang Q, Deng W, Wang Y. Synthesis of lower olefins by hydrogenation of carbon dioxide over supported iron catalysts. Catalysis Today, 2013, 215(41): 186–193
Bonura G, Cordaro M, Spadaro L, Cannilla C, Arena F, Frusteri F. Hybrid Cu-ZnO-ZrO2/H-ZSM5 system for the direct synthesis of DME by CO2 hydrogenation. Applied Catalysis B: Environmental, 2013, 140–141: 16–24
Martin O, Martin A J, Mondelli C, Mitchell S, Segawa T F, Hauert R, Drouilly C, Curulla-Ferre D, Perez-Ramirez J. Indium oxide as a superior catalyst for methanol synthesis by CO2 hydrogenation. Angewandte Chemie International Edition, 2016, 55(21): 6261–6265
Xu G, Zhang P, Cheng J, Wei T, Zhu X, Yang F. Preparation of a hollow HZSM-5 zeolite supported molybdenum catalyst by desilication-recrystallization for enhanced catalytic properties in propane aromatization. Journal of Solid State Chemistry, 2021, 300(6): 122238–122247
Odedairo T, Balasamy R J, Al-Khattaf S. Toluene disproportionation and methylation over zeolites TNU-9, SSZ-33, ZSM-5, and mordenite using different reactor systems. Industrial & Engineering Chemistry Research, 2011, 50(6): 3169–3183
Lyons T W, Guironnet D, Findlater M, Brookhart M. Synthesis of p-xylene from ethylene. Journal of the American Chemical Society, 2012, 134(38): 15708–15711
Chen Z, Ni Y, Zhi Y, Wen F, Zhou Z, Wei Y, Zhu W, Liu Z. Coupling of methanol and carbon monoxide over H-ZSM-5 to form aromatics. Angewandte Chemie International Edition, 2018, 57(38): 12549–12553
Dong P, Zhang Y, Li Z, Yong H, Li G, Ji D. Enhancement of the utilization of methanol in the alkylation of benzene with methanol over 3-aminopropyltriethoxysilane modified HZSM-5. Catalysis Communications, 2019, 123: 6–10
Gao K, Li S, Wang L, Wang W. Study of the alkylation of benzene with methanol for the selective formation of toluene and xylene over Co3O4-La2O3/ZSM-5. RSC Advances, 2015, 5(56): 45098–45105
Wang Y, He X, Yang F, Su Z, Zhu X. Control of framework aluminum distribution in MFI channels on the catalytic performance in alkylation of benzene with methanol. Industrial & Engineering Chemistry Research, 2020, 59(30): 13420–13427
Wang Y, Xu S, He X, Yang F, Zhu X. Regulating the acid sites and framework aluminum siting in MCM-22 zeolite to enhance its performance in alkylation of benzene with methanol. Microporous and Mesoporous Materials, 2022, 332: 111677–111688
Zhu Z, Chen Q, Zhu W, Kong D, Li C. Catalytic performance of MCM-22 zeolite for alkylation of toluene with methanol. Catalysis Today, 2004, 93(9): 321–325
Li Y, Yan T, Junge K, Beller M. Catalytic methylation of C-H bonds using CO2 and H2. Angewandte Chemie International Edition, 2014, 53(39): 10476–10480
Ting K W, Kamakura H, Poly S S, Toyao T, Hakim Siddiki S M A, Maeno Z, Matsushita K, Shimizu K I. Catalytic methylation of aromatic hydrocarbons using CO2/H2 over Re/TiO2 and H-MOR catalysts. ChemCatChem, 2020, 12(8): 2215–2220
Ting K W, Kamakura H, Poly S S, Takao M, Siddiki S M A H, Maeno Z, Matsushita K, Shimizu K I, Toyao T. Catalytic methylation of m-xylene, toluene, and benzene using CO2 and H2 over TiO2-supported Re and zeolite catalysts: machine-learning-assisted catalyst optimization. ACS Catalysis, 2021, 11(9): 5829–5838
Ting K W, Imbe T, Kamakura H, Maeno Z, Siddiki S M A H, Matsushita K, Shimizu K I, Toyao T. Catalytic methylation of benzene over Pt/MoOx/TiO2 and zeolite catalyst using CO2 and H2. Chemistry Letters, 2022, 51(2): 149–152
Zuo J, Chen W, Liu J, Duan X, Yuan Y. Selective methylation of toluene using CO2 and H2 to para-xylene. Science Advances, 2020, 6(34): eaba5433
Miao D, Pan X, Jiao F, Ji Y, Hou G, Xu L, Bao X. Selective synthesis of para-xylene and light olefins from CO2/H2 in the presence of toluene. Catalysis Science & Technology, 2021, 11(13): 4521–4528
Liu X, Pan Y, Zhang P, Wang Y, Xu G, Su Z, Zhu X, Yang F. Alkylation of benzene with carbon dioxide to low-carbon aromatic hydrocarbons over bifunctional Zn-Ti/HZSM-5 catalyst. Frontiers of Chemical Science and Engineering, 2021, 16(3): 384–396
Liu C, Lee S, Su D, Zhang Z, Pfefferle L, Haller G L. Synthesis and characterization of nanocomposites with strong interfacial interaction: sulfated ZrO2 nanoparticles supported on multiwalled carbon nanotubes. Journal of Physical Chemistry C, 2012, 116(41): 21742–21752
Shannon R D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica Section A, 1976, 32(5): 751–767
Deng X, Lü M, Meng J. Effect of heavy doping of nickel in compound Mo3Sb7: structure and thermoelectric properties. Journal of Alloys and Compounds, 2013, 577(15): 183–188
Kumar N, Kishan H, Rao A, Awana V P S. Fe ion doping effect on electrical and magnetic properties of La0.7Ca0.3Mn1−xFexO3 (0 ⩽ x ⩽ 1). Journal of Alloys and Compounds, 2010, 502(2): 283–288
Xie S, Iglesia E, Bell A T. Water-assisted tetragonal-to-monoclinic phase transformation of ZrO2 at low temperatures. Chemistry of Materials, 2000, 12(8): 2442–2447
Li M, Feng Z, Ying P, Xin Q, Li C. Phase transformation in the surface region of zirconia and doped zirconia detected by UV Raman spectroscopy. Physical Chemistry Chemical Physics, 2003, 5(23): 5326–5332
Song H, Laudenschleger D, Carey J J, Ruland H, Nolan M, Muhler M. Spinel-structured ZnCr2O4 with excess Zn is the active ZnO/Cr2O3 catalyst for high-temperature methanol synthesis. ACS Catalysis, 2017, 7(11): 7610–7622
Dong J J, Zhang X W, You J B, Cai P F, Yin Z G, An Q, Ma X B, Jin P, Wang Z G, Chu P K. Effects of hydrogen plasma treatment on the electrical and optical properties of ZnO films: identification of hydrogen donors in ZnO. ACS Applied Materials & Interfaces, 2010, 2(6): 1780–1784
Wang J, Li G, Li Z, Tang C, Feng Z, An H, Liu H, Liu T, Li C. A highly selective and stable ZnO-ZrO2 solid solution catalyst for CO2 hydrogenation to methanol. Science Advances, 2017, 3(10): e1701290
Chai Y, Li L, Lu J, Li D, Shen J, Zhang Y, Liang J, Wang X. Germanium-substituted Zn2TiO4 solid solution photocatalyst for conversion of CO2 into fuels. Journal of Catalysis, 2019, 371: 144–152
Xiao F X. Construction of highly ordered ZnO-TiO2 nanotube arrays (ZnO/TNTs) heterostructure for photocatalytic application. ACS Applied Materials & Interfaces, 2012, 4(12): 7055–7063
Liu Y, Xia C, Wang Q, Zhang L, Huang A, Ke M, Song Z. Direct dehydrogenation of isobutane to isobutene over Zn-doped ZrO2 metal oxide heterogeneous catalysts. Catalysis Science & Technology, 2018, 8(19): 4916–4924
Wang B, Chen B, Sun Y, Xiao H, Xu X, Fu M, Wu J, Chen L, Ye D. Effects of dielectric barrier discharge plasma on the catalytic activity of Pt/CeO2 catalysts. Applied Catalysis B: Environmental, 2018, 238: 328–338
Ou G, Xu Y, Wen B, Lin R, Ge B, Tang Y, Liang Y, Yang C, Huang K, Zu D, Yu R, Chen W, Li J, Wu H, Liu L M, Li Y. Tuning defects in oxides at room temperature by lithium reduction. Nature Communications, 2018, 9(1): 1302–1311
Wang N, Li S, Zong Y, Yao Q. Sintering inhibition of flamemade Pd/CeO2 nanocatalyst for low-temperature methane combustion. Journal of Aerosol Science, 2017, 105: 64–72
Liu X, Wang M, Zhou C, Zhou W, Cheng K, Kang J, Zhang Q, Deng W, Wang Y. Selective transformation of carbon dioxide into lower olefins with a bifunctional catalyst composed of ZnGa2O4 and SAPO-34. Chemical Communications (Cambridge), 2018, 54(2): 140–143
Cheng K, Zhou W, Kang J, He S, Shi S, Zhang Q, Pan Y, Wen W, Wang Y. Bifunctional catalysts for one-step conversion of syngas into aromatics with excellent selectivity and stability. Chem, 2017, 3(2): 334–347
Acknowledgments
This project was sponsored financially by the National Natural Science Foundation of China (Grant No. 21776076) and the Fundamental Research Funds for the Central Universities (Grant No. JKA01211710).
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Cheng, J., Zhao, Y., Xu, G. et al. ZnxZr/HZSM-5 as efficient catalysts for alkylation of benzene with carbon dioxide. Front. Chem. Sci. Eng. 17, 404–414 (2023). https://doi.org/10.1007/s11705-022-2215-6
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DOI: https://doi.org/10.1007/s11705-022-2215-6